Acetic acid manufacture



Patented July 14, 1936,

'D0 waulree. Wia, a corporation of New York cation April 19, 1935,

. Serial No. 11,332 1;; Claims. (c1. 260116) The invention relates to the manufacture of Another object of the invention is to provide a method for the manufacture of acetic. acid from dilute mixtures of acetaldehyde by oxidation of the acetal ehy idizing fluids. A still further object is to provide taining various other constituents with various catalysts.

Another object is to provide a process wherein the acetic acid formed may be removed at temperatures materially below the boiling point of acetic acid.

to intimate contact. appear hereinafter.

The catalyst which is preferably used in accor-dance with our invention and which is also used and described in our parent U. S. application, filed May 7, 1932, now U. S. Patent No.

In place of cobaltous acetate,- other salts such as cobalt carbonate, cobalt oxide and the like my in the activation of the catalyst solution may be larger than the quantity employed when acid formation is being carried out.

It is to be noted that our cobaltic acetate oxidation catalyst, its composition and its method cobaltic acetate catalyst, excepting wherein the claims specifically include this feature.

In making acetic acid in accordance with the invention, dilute acetaldehyde and oxygen, air.

or other oxygen-containing gases, are dispersed in intimate contact with the catalyst solution.

2 the catalyst solution.

various other ways of introducing the diluted acetaldehyde and oxidizing medium which are satisfactory. For example, the acetaldehyde and oxidizing medium can be introduced through separate conduits, which converge or meet in the vicinity of the catalyst solution, thereby permitting intimate contact of the aldehyde and oxidizing medium in their e through the catalyst solution.

It being desirable to provide as extensive contact as possible between the catalyst and the gas, a convenient method consists of dispersing the gas mixture as small bubbles through the catalyst solution, for example by passing the gas into the lower level of the solution through extremely small pores, such as a porous alundum plate. However, other intimate contact of catalyst and reacting gases, such as spraying the catalyst into the gas may be used.

The velocity of the reaction is sufficiently rapid to permit the use of relatively short contact periods, say about 6 to 18 seconds, but longer contact periods are not harmful, since the acetic acid and other products of the process are not vigorously acted on by the catalyst solution. Shorter periods may be used. but materially shorter periods give lower conversion of acetaldehyde to acetic acid.

One of the most important advantages of our method for the production of acetic acid is that it which merely contain acetaldehyde of acetic acid without requiring a preliminary separation of the'acetaldehyde from the other constituents of the gas mixture. Prior to our invention, it was generally considered desirable, if not necessary, in processes of producing acetic acid, by the catalytic oxidation of acetaldehyde to employ concentrated acetaldehyde, namely, sources of acetaldehyde comprising 85-90% or more of acetaldehyde. To obtain such acetaldehyde may require the trouble and expense of concentration, redistillation and other treatment.

We have found that not only is the use of concentrated acetaldehyde unnecessary, but that diluted acetaldehyde, which is more readily obtainable and less costly, will give satisfactory results and when employed in certain ranges of dilution will give desirable results to be described hereinafter, not obtainable with concentrated acetaldehyde.

with some of the present known methods for the production of acetaldehyde it is obtained as one constituent of a gas mixture which contains other gases, such as hydrogen, nitrogen, carbon monoxide, carbon dioxide and hydrocarbon gases. According tothe method of this invention, such acetaldehyde-containing gas mixtures are mixed with the appropriate quantity of oxygen, air, or other oxygen-containing gas and passed into a catalyst solution in which the acetaldehyde is oxidized to acetic acid, while the other constituents of the gas mixture pass through. Or, as previously indicated, the dilute acetaldehyde and oxidizing medium may be supplied separately to the catalyst solution.

Excellent results have been obtained with gas mixtures which contained as little as 2% acetaldehyde. With the lean mixtures, it is generally desirable to employ a larger excess of oxygen than with the mixtures which contain a larger percentage of acetaldehyde. The lean gas mixture could oxygen for While this feature of pre-- mixing the dilute acetaldehyde and oxidizing mebe prepared by diluting concentrated acetaldehyde and oxygen, or concentrated acetaldehyde and air. but it is not necessary to obtain concentrated acetaldehyde and dilute it for oxidation,

' since this method for the production of acetic acid satisfactorily efiects the oxidation of commercially obtainable lean mixtures of acetaldehyde.

The following examples are illustrative of the manner and method of practicing the invention, and of the results which have been obtained by the use of lean or diluted gaseous mixtures containing acetaldehyde.

I. A good grade of substantially concentrated acetaldehyde was mixed with air. The gas mixture resulting, composed of 26.5% acetaldehyde by volume and the remainder air, was continuously bubbled through a porous alundum partition into a catalyst solution containing approximately 2% cobaltic acetate in acetic acid. The catalyst was heated to 65 C. It was found that about 91% of the acetaldehyde was converted into acetic acid, about 0.5% was not attacked, and the remainder was decomposed mainly to carbon dioxide and water. The velocity of the reaction was relatively rapid, about 6-18 seconds contact of gas and catalyst being amply sufficient.

II. A gas mixture composed of 4.6% acetaldehyde, 2.9% oiwgen and 92.5% hydrogen by volume was bubbled through an alundum partition into a catalyst solution of 2% cobaltic acetate in glacial acetic acid, which was heated to about 56 C. This gas mixture contained an excess of about 30%-oxygen over the theoretical requirement of the oxidation of all the acetaldehyde to acetic acid. The vapor space upper portion of the catalyst solution were heated to about C. and the condensable vapors were condensed in a condenser. About 93% of the acetaldehyde yielded acetic acid, about 1% was unchanged and about 6% was decomposed into noncondensable gases. The contact of gases and catalyst was about that which was described in Example I.

III. A gas mixture composed of 5.7% acetaldehyde by volume, 3.1% ethylene, 1.2% acetylene, 49% methane and 37% hydrogen was mixed with sufllcient air to supply a 100% excess of oxygen over the theoretical amount necessary to combine with the acetaldehyde and produce acetic acid. The mixed gas was bubbled through an alundum partition into a 2% catalyst solution of' cobaltic acetate in glacial acetic acid, which was heated to a reaction temperature of 65-70 C. The vapor space over and the upper portion of the catalyst solution were maintained at about 43 C. About 90% of the acetaldehyde was convertedto acetic acid, a fractional percentage was unconverted and the remainder was changed into a non-condensable gas.

The above Examples 11 and III show that when employing an inexpensive source of acetaldehyde containing only around 5% acetaldehyde, but diluted with other constituents, such as methane, ethylene, acetylene and hydrogen, the percentage conversion to acetic acid was as high or higher than when a substantially concentrated acetaldehyde was employed.

It will be further observed that, even though acetic acid has a boiling point of about 118 C., by virtue of the partial pressure effect of the constituents, such as ethylene, methane, acetylene, hydrogen and other diluent gases, on the partial pressure of the acetic acid, it is possible to remove the acetic acid formed at temperatures materlally below 118 0., namely the boiling point of In the specification and claims, where we refer acetic acid. The particular temperature required to dilute or lean acetaldehyde or. diluted gaseous will be dependent on the volume of diluent gases mixtures of acetaldehyde, we refer to a source of present, but in the examples described and in all acetaldehyde comprised only in part of acetalde- 5 instances where material volumes of ethylene, hyde and containing material quantities of dilu- 5 carbons were present, the temperature required ra rocarbons, hydrogen and the like. will be well below 80 C. is important in We at it more practical and economical to oper- 1. The method of making acetic acid from a ate an oxidation tower at these temperatures hydrocarbon diluted gaseous mixture of acetalde- 1 The acetic acid which is formed by the oxidahyde which comprises passing the dilute gaseous tion of the acetaldehyde in the catalyst solution mixture of acetaldehyde into an acetic acid solumay be allowed to accumulate in the catalyst solution of a metal acetate catalyst, supplying oxygen tion for a time and then separated from the cataby introducing air into the catalyst and oxidizing l5 lyst by distillation, extraction or other suitable the acetaldehyde in the dilute mixture of aceta1- dehyde.

facture of acetic acid, which is described and air to form an acetaldehyde-air mixture and 20 claimed in our above named U. S. Patent No. passing the mixture in contact with an acetic 1,976,756 and which is generic to this appllcaacid solution of a metal acetate maintained at a tion in certain respects; in other features, this temperature between about 50 C. to about 80 C.

thereof. See also Patent No. 1,976,757, of October comprises oxidizing with free oxygen hydrocar- 25 filed May 7, 1932, for a method of manufacturing catalyst comprising essentially a solution in cobaltic acetate, to which the instant application acetic acid containing around 6% of water, of is related. v The oxidation of diluted acetaldehyde can be amount of cobaltic acetate which will give a 30 e water, cobaltic acetate and acetic acid in the The method of making acetic acid from a substances may be present. The concentration hyde which comprises passing the dilute gaseous of cobaltic acetate may range from a few tenths mixture of acetaldehyde into an acetic acid solu- 35 of 1% to saturated solutions. A satisfactory tion of a metal acetate catalyst, supplying oxygen catalyst may be made by dissolving 2 grams of by introducing into the catalyst solution a gas cobaltous acetate containing four molecules of which contains free oxygen, and oxidlzmg the water of crystallization in 100 cubic centimeters acetaldehyde in the dilute mixture of acetalde- 40 of substantially glacial acetic acid which cone. 40

this solution in the specification and claims as an 75% of acetaldehyde, the remainder of the mix- 45 contain the catalyst solution and into which the free oxygen, and oxidizing the acetaldehyde in the .50 e.

ent No. 1,976,756. Or the oxidation may be carof acetaldehyde, the remainder of the mixture 55 column and progressing down the column counbetween about 50 C. to about 80 C. and supply- 60 ter-current to the rising dilute acetaldehyde, ing free oxygen by introducing air into the which may be introduced at or near the bottom of catalyst solution. 7 the column. 7. The process of preparing acetic acid from While we prefer to employ our new cobaltic a dilute gaseous mixture containing from 2% to acetate catalyst in producing acetic acid from diless than 40% of acetaldehyde which comprises 65 lute acetaldehyde because of the very high conpassing the dilute gaseous mixture of acetaldetion catalysts. Consequently, our invention emand about 70 C. and supplying free oxygen 7 braces the catalytic conversion of lean acetaldewhereby acetic acid is formed and employing hyde with other catalysts such as acetates of temperatures materially below 100 C. to recover manganese, vanadium, cerium and nickel, for exacetic acid from the catalyst solution by vaporiample, when applying the features described zation.

5 above. 8. The process of producing acetic acid which solution changes to a greenish brown or black. thereafter pass ng a gaseous mixture comprised only in part of acetaldehyde in contact with the activated solution, supplying oxygen by introducing into the catalyst solution a gas which contains oxygen, and oxidizing the acetaldehyde in the gaseous mixture.

9. The method of manufacturing acetic acid which comprises forming a catalyst solution by dissolving acetic acid, activating this solution by contacting amixture of acetaldehyde and a considerable excess of air therewith until at least a part of the cobaltous salt is converted to the cobaltic state, thereafter as a dilute gaseous mixture of acetaldehyde in contact with the activated catalyst solution, supplying oxygen by introducing a quantity of air less than a considerable excess into the catalyst solution, and oxidizing the acetaldehyde in the dilute gaseous mixture of acetaldehyde.

10. A catalyst for the production of acetic acid which comprises essentially a substantially glacial acetic acid solution of cobaltic acetate and which has been activated by aldehyde and free oxygen 'vating this solution by contacting 11. A catalyst solution for the production of acetic acid which comprises essentially a solution 01 acetic acid containing from about 1% to 10% of water, of irom a few tenths 1% of cobaltic acetate to an amount of cobaltic acetate 5 which will give a saturated solution at room temperature and which has been activated with aldehyde and a considerable excess 01 air.

12. A method (or manufacturing acetic acid which comprises forming a catalyst solution by dissolving a cobaltous salt in acetic acid, actia mixture 0! acetaldehyde and a considerable excess'ot air therewith until at least a part of the cobaltous salt is converted to the cobaltic state, thereafter passing acetaldehyde in contact with the activated catalyst solution, supplying oxygen by introducing a quantity of air less than a considerable excess into the catalyst solution, dizing the acetaldehyde to acetic acid. 13. A catalyst solution for producing acetic acid from dilute acetaldehyde comprising an acetic acid solution of cobaltlc acetate which contains above 134% normality of cobaltic ion and which has been subjected to an activation treatment with acetaldehyde and a considerable excess of air.

ULRICH KOPSCHp WALTER O. WALKER. 

